Magnesium-based controlled-release hydrogen embedding wire as well as preparation method and application thereof

Abstract

The invention discloses a magnesium-based controlled-release hydrogen embedding wire and a preparation method and application thereof, the magnesium-based controlled-release hydrogen embedding wire is formed by in-situ controlled hydrogenation of a magnesium wire or a magnesium-based alloy wire, and can be used for preparing an embedding wire therapy instrument; the purity of the magnesium wire is more than 99%; the magnesium-based alloy wire is made of conventional biodegradable magnesium-based alloy, and the conventional biodegradable magnesium alloy comprises but is not limited to Mg-Al, Mg-Zn, Mg-Re, Mg-Mn, Mg-Ca, Mg-Li, Mg-Sr, Mg-rare earth elements and the like. The diameter of the magnesium wire or the magnesium-based alloy wire is 0.1-0.5 mm, and the controlled hydrogenation ratio is larger than 0 and smaller than 80%. According to the magnesium-based controlled-release hydrogen embedded suture, the hydrogen release rate can be effectively regulated and controlled, suture embedding materials and degradation products are safe, and systematic side effects are reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of medical devices, and in particular to a magnesium-based controlled hydrogen-release embedded wire and a preparation method and application thereof. Background Art

[0002] Acupoint thread embedding therapy, guided by Traditional Chinese Medicine (TCM) theory and based on the theories of internal organs, meridians, qi and blood, combines traditional acupuncture with modern medical technology. Based on the specific symptoms of the condition, specific materials are implanted into acupoints to stimulate qi and blood in the meridians, improve body function, regulate the internal organs, balance yin and yang, dredge the meridians, and harmonize qi and blood. Traditional acupoint thread embedding often uses materials such as absorbable catgut and surgical sutures, but these materials are quickly absorbed into the body and their stimulating effects do not last long, necessitating frequent treatments. Furthermore, these materials have relatively poor biocompatibility and are prone to allergic reactions or local inflammatory reactions. Due to rejection of traditional thread embedding, patients are prone to adverse reactions such as redness, swelling, pain, increased skin temperature, and localized tissue necrosis and cavity formation at the implantation sites.

[0003] As catgut implantation therapy continues to gain clinical application, the materials used are constantly being updated, and researchers are exploring new materials to overcome the shortcomings of traditional materials. Currently, commonly used new catgut implantation materials, such as poly(lactic acid) (PGLA), are synthetic fibers formed by copolymerizing poly(lactic acid) and poly(glycolic acid) in a certain ratio. They exhibit minimal tissue reactions, are less susceptible to immune rejection, and possess good flexibility and degradability. Another example is poly(dioxanone) (PPDO), which takes a long time to degrade in the body and has a longer-lasting stimulating effect. It can be completely decomposed into carbon dioxide and water, making it suitable for long-term catgut implantation therapy. However, the primary therapeutic mechanism of these catgut implantation materials is to replace the physical stimulation of acupuncture, resulting in relatively simple therapies and lacking other therapeutic options. Regarding improved methods for traditional catgut implantation therapy, for example, invention CN105497778B discloses a method for preparing catgut for acupuncture points for Qi and Blood Deficiency in Alzheimer's disease. Catgut, soaked in a filtrate of the drug, is implanted at the corresponding acupuncture points on the patient's body to synergistically enhance the therapeutic effects of catgut implantation alone on the meridians and acupuncture points. However, although the above-mentioned thread embedding therapy has expanded its therapeutic applications, the traditional thread embedding materials used are still prone to cause inflammatory reactions in biological tissues, resulting in allergies and infections.

[0004] Magnesium degrades more rapidly in acidic environments, and many pathological conditions (such as chronic inflammation and ischemia-reperfusion injury) are accompanied by a decrease in local pH. This pH-responsive release mechanism enables magnesium hydrogen catgut implants to automatically increase the rate of hydrogen release in the affected area, thereby adapting to different treatment needs and enhancing therapeutic efficacy. Current research demonstrates that through the controlled degradation of magnesium hydrogen catgut implants, hydrogen can be efficiently released locally within the tumor, creating a high-concentration hydrogen environment and thus enhancing anti-tumor efficacy. Compared to traditional methods of inhaled or oral administration of hydrogen, this approach allows for better targeting of the target area. Localized hydrogen delivery avoids the side effects of high-dose systemic administration, reduces potential toxic reactions, minimizes the effects on healthy tissue, and offers a higher safety profile. Furthermore, in the acidic microenvironment of trauma or surgery, the rapid release of hydrogen helps mitigate inflammation and oxidative damage. By delivering hydrogen locally, magnesium hydrogen catgut implants significantly reduce systemic exposure and potential systemic toxicity, while minimizing the effects on healthy tissue and improving safety. This targeted therapeutic strategy is particularly useful in treatments requiring prolonged or high-dose hydrogen administration.

[0005] For example, CN109652691B discloses a metal implantable lead, its preparation method, and its application. The implantable lead, measured by weight percentage (100%), consists of a metal M and an element X, where 90% ≤ metal M ≤ 100%, and the remainder is element X. M is at least one of magnesium or zinc, and X is at least one of a nonmetallic element, a main-group alkali metal element, a main-group alkaline earth metal element, a Group VIII element, or a sub-group metal element. In this invention, magnesium or zinc is the primary metal material used in the preparation of the metal implantable lead, along with other nonmetallic elements, alkali metals, alkaline earth metals, and Group VIII elements, to achieve a certain biodegradability through alloy composition adjustment. While this material exhibits a certain degree of biocompatibility and an appropriate degradation rate during in vivo degradation, it fails to address the role of hydrogen and lacks precise control over hydrogen release.

[0006] Invention CN112672698B discloses a thread for thread embedding therapy and a needle device for thread embedding therapy including the same. The thread for thread embedding therapy comprises a linear core comprising a biodegradable polymer; and a metal wire spirally wound around the outer circumference of the linear core. The metal wire comprises a biodegradable metal primarily composed of magnesium or zinc. When applied to the human body for thread embedding therapy, the metal wire has no side effects on biological tissue and can enhance tissue traction. The biodegradable metal, when used in thread embedding therapy, has the properties of being absorbed and decomposed within tissue, releasing metal ions and decomposition products. Biodegradable metals such as magnesium (Mg), calcium (Ca), and zinc (Zn), as alkaline earth metals, react with water to generate hydrogen. This hydrogen generation reduces the contact area between the biodegradable polymer linear core and tissue, ultimately increasing the thread's residual life within the tissue. The hydrogen generated within the tissue also imparts a swelling effect. This invention uses biodegradable metal to wrap around biodegradable polymer to obtain an embedded wire, and uses the metal reaction to release hydrogen. However, its embedded wire structure and preparation process are complex, the embedded wire operation is inconvenient, and the manufacturing and use costs are high. In addition, this invention hopes to extend the residual life of the wire in the tissue by generating hydrogen through metal reaction, and does not involve the sustained release of metal materials and the regulation of hydrogen release rate.

[0007] Therefore, how to provide a magnesium-based embedded thread to achieve precise control of the hydrogen release rate, reduce systemic side effects, enhance the efficacy of targeted treatments such as anti-inflammatory and anti-tumor, and play an effective role in the preparation of beauty and health care embedded thread therapy devices is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0008] In response to the defects in the existing technology, the present invention provides a magnesium-based controlled hydrogen-release embedded wire, its preparation method and application. Through the innovative design of controlled hydrogenation of magnesium wire or magnesium-based alloy wire, while solving the problems of poor controllable degradation and poor biocompatibility of traditional materials, by effectively controlling the hydrogen release rate, it achieves targeted treatment effects in local pathological environments, and is promoted and applied in multiple fields such as facial beauty and local obesity.

[0009] In a first aspect, the present invention provides a magnesium-based controlled hydrogen-release buried wire, wherein the magnesium-based controlled hydrogen-release buried wire is formed by in-situ controlled hydrogenation of a magnesium wire or a magnesium-based alloy wire;

[0010] The purity of the magnesium wire is above 99%;

[0011] The magnesium-based alloy includes at least one of a magnesium-based binary alloy and a magnesium-based multi-component alloy;

[0012] The diameter of the magnesium wire or magnesium-based alloy wire is 0.1-0.5 mm, and the controlled hydrogenation ratio is greater than 0 and less than 80%.

[0013] The present invention uses magnesium or a magnesium-based alloy as the primary metal material for the implantable wire. The magnesium wire used has a purity of over 99%, preferably over 99.5%, and more preferably over 99.9%. It possesses excellent biocompatibility and biodegradability, making it widely used in medical applications. Its degradation products are hydrogen and magnesium hydroxide, both harmless substances that help reduce allergic reactions and infections that may be associated with traditional materials. Compared to traditional magnesium materials, the addition of other metal elements (such as Zn and Nd) can further optimize its performance, particularly enhancing its degradation characteristics, hydrogen release capacity, and biological effects.

[0014] Preferably, after in-situ controlled hydrogenation, the magnesium-based controlled hydrogen-release embedded wire has a hydrogenated shell covering the outer surface of the magnesium wire or magnesium-based alloy wire along the length direction, and the ratio of the radial thickness R1 of the hydrogenated shell to the radius R2 of the internal unhydrogenated magnesium wire or magnesium-based alloy wire satisfies: 0<R1 / R2≤4.5.

[0015] Magnesium metal, due to its rapid hydrogen release rate, is suitable for treatments requiring a rapid response, but it can also cause localized overreactions and side effects. Therefore, the present invention utilizes in-situ controlled hydrogenation of magnesium metal to form a hydrogenated shell on the outer surface of a magnesium wire or magnesium-based alloy wire. This hydrogenated shell provides more controlled and sustained hydrogen release, making it suitable for treatments requiring long-term, stable hydrogen release, particularly in the treatment of tumors, wound repair, and chronic inflammation.

[0016] Preferably, the magnesium-based alloy wire meets at least one of the following conditions:

[0017] 1) The magnesium-based alloy is a magnesium-based binary alloy, including at least one of Mg-Al, Mg-Zn, Mg-Re, Mg-Mn, Mg-Ca, Mg-Li, Mg-Sr, and Mg-rare earth elements;

[0018] 2) The magnesium-based alloy is a magnesium-based binary alloy Mg x Zn a and Mg x Nd b combination of;

[0019] 3) The magnesium-based alloy is a magnesium-based ternary alloy Mg x Zn a Nd b .

[0020] Preferably, the Mg-rare earth element includes but is not limited to at least one of Mg-Nd, Mg-Sc, and Mg-Er.

[0021] Preferably, the magnesium-based alloy wire satisfies at least one of the following conditions:

[0022] 1) In the magnesium-based alloy wire, the Mg content is 95-98 at.%, the Zn content is 0.5-3 at.%, and the Nd content is 0.5-3 at.%;

[0023] 2) In the hydrogenation shell, at least Mg, MgH2, MgZn2 and NdH y phase, and the NdH y The grain size is 5-20nm and is dispersed inside and on the surface of Mg.

[0024] Zinc is a commonly used bioalloying element that promotes cell growth and repair. Its addition can regulate the degradation rate of magnesium, thereby increasing the stability of hydrogen release and reducing the problem of magnesium degradation being too rapid or too slow in the body. Zinc also enhances the material's corrosion resistance, extending the lifespan of magnesium-based alloys in the body.

[0025] Neodymium, a rare earth element, possesses strong antioxidant properties, enhancing the material's mechanical strength and biocompatibility. During hydrogen release, neodymium helps increase the release rate and optimize the distribution of hydrides (such as the NdHy phase), further improving the material's stability. Neodymium can also effectively reduce localized oxidation and enhance the material's biotolerance, particularly in the treatment of inflammation and trauma, reducing adverse reactions.

[0026] The magnesium-based binary alloy and magnesium-based multi-element alloy of the present invention can precisely regulate the rate of hydrogen release by rationally matching elements such as Zn and Nd in the magnesium-based alloy. This makes hydrogen release more stable and sustained, and can be adaptively adjusted according to local pathological environments, such as acidic microenvironments, thereby achieving targeted treatment. Secondly, the biocompatibility of the alloy is enhanced: after the addition of Zn and Nd elements, the corrosion resistance and mechanical strength of the alloy are improved, which can reduce side effects such as allergies and inflammation that may be caused by traditional materials, promote tissue repair, reduce rejection reactions, and improve patient tolerance.

[0027] In particular, compared with single magnesium material, Mg x Zn a Nd b Through the combination of multiple metal elements, the alloy not only provides long-term and stable hydrogen release, but also has stronger antioxidant and anti-inflammatory effects, thereby enhancing the multiple benefits of treatment, especially in the fields of tumor treatment, wound repair and chronic inflammation, showing better therapeutic effects.

[0028] Preferably, the surface of the magnesium-based controlled hydrogen-release buried wire has a nano-slow-down layer comprising at least one of nano-magnesium oxide, nano-magnesium silicate, and nano-magnesium metasilicate, and the thickness of the nano-slow-down layer is 0.2-20 μm.

[0029] The nano slow-fall layer is prepared by the following method:

[0030] (1) dispersing the raw materials of the nano-slow-fall layer in an organic solvent (e.g., ethanol) to obtain a nano-dispersion liquid;

[0031] (2) placing the magnesium-based controlled hydrogen-release embedded wire into the nano-dispersion liquid, or spraying the nano-dispersion liquid onto the surface of the magnesium-based controlled hydrogen-release embedded wire;

[0032] (3) Drying to form the magnesium-based controlled hydrogen-release embedded wire having a nano-slow-fall layer on the surface.

[0033] The nano-slow-down layer formed by nano-scale raw materials is beneficial to isolating the internal magnesium-based controlled hydrogen-release embedded wire from the human body. Since the degradation rate of the nano-slow-down layer is slightly slower than that of the magnesium-based controlled hydrogen-release embedded wire, the progress of layer-by-layer degradation of the magnesium-based controlled hydrogen-release embedded wire in the human body can be regulated according to factors such as the thickness and density of the nano-slow-down layer to further control the hydrogen release rate. On the other hand, the nano-slow-down layer also forms a protective barrier for the internal magnesium-based controlled hydrogen-release embedded wire during transportation and storage, preventing it from damage, contamination and other unexpected losses.

[0034] Preferably, the hydrogen release rate of the magnesium-based controlled hydrogen-release embedded wire is greater than 0 and less than or equal to 10.0 ml / h×cm 2 , the hydrogen release time is greater than 0 and less than or equal to 5 weeks.

[0035] The magnesium-based controlled-release hydrogen embedded wire of the present invention can continuously release hydrogen at a desired rate within a predetermined period of use. By adjusting the material and process parameters, precise control of the hydrogen release amount and rate can be achieved, thereby meeting the specific requirements of hydrogen supply in different application scenarios.

[0036] In a second aspect, the present invention further provides a method for preparing the magnesium-based controlled hydrogen release embedded wire, comprising the following steps:

[0037] S1. smelting magnesium or magnesium-based alloy raw materials into ingots;

[0038] S2, extruding the ingot into a cylindrical billet;

[0039] S3. Drawing the blank to obtain magnesium wire or magnesium-based alloy wire;

[0040] S4. Performing an in-situ controlled hydrogenation treatment on the magnesium wire or magnesium-based alloy wire to obtain the magnesium-based controlled hydrogen-release embedded wire.

[0041] Preferably, the preparation method satisfies at least one of the following:

[0042] 1) In step S2, the ingot is heated to 150-450° C. and the punching rate is 0.2-0.5 mm / s to obtain a cylindrical billet with a diameter of 1-10 mm and a length of 10-20 mm;

[0043] 2) In step S3, the blank is subjected to multiple drawing processes to obtain a magnesium wire or a magnesium-based alloy wire with a diameter of 0.1-0.5 mm;

[0044] 3) In step S4, the magnesium wire or magnesium-based alloy wire is subjected to an in-situ controlled hydrogenation treatment using hydrogen gas at a hydrogen pressure of 0.5-10 MPa, a holding time of 1-24 h, and a temperature of 100-450° C. Alternatively, the magnesium wire or magnesium-based alloy wire is subjected to an in-situ controlled hydrogenation treatment using hydrogen plasma irradiation for a time of 1-60 min, preferably 1-30 min.

[0045] Under vacuum conditions (e.g. about 10 -4 The present invention utilizes two in-situ controlled hydrogenation methods to treat magnesium wire and magnesium-based alloy wire. In comparison, the direct hydrogenation reaction between hydrogen and wire in a high-temperature environment requires relatively simple equipment and operation.

[0046] Hydrogen plasma treatment, on the other hand, offers relatively mild conditions. Because the active hydrogen particles in hydrogen plasma have strong reducing properties, hydrogen plasma can react with magnesium to produce magnesium hydride (MgH2) at temperatures below 100°C, preferably below 80°C, and more preferably between room temperature and 50°C. This process utilizes the high energy and activity of plasma technology, enabling the hydrogenation reaction to proceed at lower temperatures, thereby improving reaction efficiency and rate. Hydrogen plasma can be either microwave plasma (a plasma excited by microwaves) or radio frequency plasma (a plasma excited by radio frequency). These plasmas can be pulsed or direct current excited. Microwave plasma generates a high-density, extensive, non-equilibrium hydrogen plasma, which facilitates the production of magnesium hydride. Microwave power can be selected to be above 300 W, and microwave frequency can be selected to be above 0.5 GHz, for example, between 1 and 20 GHz. The excitation frequency used in generating radio frequency plasma is generally above 10 MHz. The reaction atmosphere for hydrogen plasma is typically hydrogen or a mixture of hydrogen and argon, for example, with a volume ratio of hydrogen to argon of (20-50):(50-80). Hydrogen as the reaction gas and argon as the carrier gas help maintain plasma stability and activity. A hydrogen concentration above 30% v / v is suitable for rapid and efficient surface hydrogenation, but the irradiation time must be strictly controlled below 30 minutes to avoid excessive hydrogenation and structural collapse of the magnesium wires, which can lead to a decrease in mechanical properties. Lower hydrogen concentrations, on the other hand, are suitable for slow and uniform hydrogenation, which helps maintain good mechanical properties.

[0047] Preferably, in step S3, after the drawing process, the following steps are further included:

[0048] S3.1. Anneal the magnesium wire or magnesium-based alloy wire under inert gas protection and cut it into coarse alloy wires with a length of 0.1-1.0 cm;

[0049] S3.2, polishing the cut rough alloy wire to obtain a polished alloy wire;

[0050] S3.3. Treat the polished alloy wire with acid, clean and dry it to obtain the magnesium wire or magnesium-based alloy wire.

[0051] After step S4, there is also a step of forming a nano slow-down layer on the surface of the magnesium-based controlled hydrogen-release buried wire, including:

[0052] 1) dispersing the raw materials of the nano-slow-fall layer in an organic solvent (such as ethanol) to obtain a nano-dispersion liquid;

[0053] 2) applying (e.g., dipping, spraying, coating, etc.) the nano-dispersion onto the surface of the magnesium-based controlled hydrogen-release embedded wire;

[0054] 3) Drying to form a magnesium-based controlled hydrogen-release embedded wire with a nano-slow-fall layer on the surface.

[0055] In a third aspect, the present invention further provides a use of the magnesium-based controlled hydrogen-release catgut embedding method, or the magnesium-based controlled hydrogen-release catgut embedding method obtained by the preparation method, for preparing a catgut embedding therapy device.

[0056] The present invention has at least the following beneficial effects:

[0057] (1) The magnesium-based controlled hydrogen-release buried wire of the present invention is formed by in-situ controlled hydrogenation of high-purity magnesium wire and magnesium-based alloy wire, and the magnesium-based alloy is conventional magnesium-based alloy and multi-element magnesium-based alloy, including but not limited to Mg-Al, Mg-Zn, Mg-Re, Mg-Mn, Mg-Ca, Mg-Li, Mg-Sr, Mg-rare earth elements (such as Mg-Sc, Mg-Nd), Mg x Zn a Nd b Its specific composition and proportion can be adjusted within a reasonable range according to actual needs. This not only regulates the release rate of hydrogen, but also effectively achieves stable and sustained release of hydrogen in local pathological environments (such as tumors, trauma, chronic inflammation, etc.) or functional thread embedding areas (such as thread lifts, barbed threads, repair and cosmetic procedures, etc.), thus solving the problems of traditional magnesium-based materials with excessively rapid hydrogen release rates, strong local reactions, and significant side effects. The slow release of hydrogen not only ensures local safety but also provides long-term and stable therapeutic effects for targeted therapies, showing significant advantages in the fields of tumor treatment and wound repair.

[0058] (2) By adding metal elements such as zinc and neodymium and rationally allocating their amounts, the present invention effectively improves the corrosion resistance and biocompatibility of magnesium-based alloys, reducing adverse reactions such as allergic reactions and local inflammation that may be caused by traditional magnesium materials. Zinc promotes cell repair, and neodymium has antioxidant properties. These properties make the magnesium-based implantable wire material of the present invention safer during in vivo degradation, reducing rejection reactions and promoting tissue repair. Compared with traditional materials, the implantable wire provided by the present invention can improve patient tolerance and is particularly suitable for long-term implantation.

[0059] (3) The present invention effectively regulates the hydrogen release rate and improves the stability of the material by forming a magnesium hydride shell and an optional nano-degradation layer on the surface of the magnesium-based alloy. The presence of the hydride shell prevents the rapid degradation of the magnesium metal, provides a sustained and stable hydrogen release, reduces damage to healthy tissue, and adaptively adjusts the release of hydrogen in an acidic environment, further optimizing the local therapeutic effect. This solves the problem of the excessively rapid hydrogen release rate of existing magnesium-based implant materials, making the material's therapeutic effect more controllable and long-lasting. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 This is a schematic structural diagram of the magnesium-based controlled hydrogen-release embedded wire of the present invention;

[0061] Figure 2 Schematic diagram of the structure of a magnesium-based controlled hydrogen release buried wire with a nano-slow-down layer;

[0062] Figure 3 The preparation process diagram of the magnesium-based controlled hydrogen release embedded wire of the present invention;

[0063] Figure 4 This is a polarization curve diagram of a partially embedded wire sample of the present invention.

[0064] Explanation of reference numerals: 1-magnesium wire, 1'-magnesium-based alloy wire, 2-hydrogenated shell, 3-nanometer slow-down layer. DETAILED DESCRIPTION

[0065] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the specification and specific implementation methods. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0066] The terms used in the embodiments of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The singular forms "a," "an," "the," and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms, and unless the context clearly indicates otherwise, "a plurality" generally includes at least two.

[0067] It should also be noted that the terms "include," "comprises," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a product or device comprising a series of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such product or device. In the absence of further limitations, an element defined by the phrase "comprises a..." does not exclude the presence of other identical elements in the product or device comprising the element.

[0068] See also Figure 1 In a first embodiment of the present invention, a magnesium wire 1 is used as a hydrogenation substrate. The magnesium-based controlled hydrogen-release buried wire is formed by in-situ controlled hydrogenation of the magnesium wire 1. The purity of the magnesium wire 1 is above 99%. The diameter of the magnesium-based controlled hydrogen-release buried wire is 0.1-0.5 mm, preferably 0.2-0.4 mm. The controlled hydrogenation ratio is greater than 0 and less than 80%, preferably 0.1-50%, and more preferably 1-30%.

[0069] After in-situ controlled hydrogenation, the magnesium-based controlled hydrogen-release embedded wire has a hydrogenated shell 2 containing magnesium hydride covering the outer surface of the magnesium wire 1 along its length. The ratio of the radial thickness R1 of the hydrogenated shell 2 to the radius R2 of the unhydrogenated magnesium wire 1 within satisfies 0 < R1 / R2 ≤ 4.5, preferably 0 < R1 / R2 ≤ 1.5. Residual unreacted Mg is not excluded in the hydrogenated shell 2, and thus Mg and MgH2 phases are present in the hydrogenated shell 2.

[0070] like Figure 2 The surface of the magnesium-based controlled hydrogen-release buried wire has a nano-slow-down layer 3, which includes at least one of nano-magnesium oxide, nano-magnesium silicate, and nano-magnesium metasilicate. The thickness of the nano-slow-down layer 3 is 0.2-20 μm.

[0071] The second embodiment uses a magnesium-based alloy wire 1' as a hydrogenation substrate, see Figure 1 The magnesium-based controlled hydrogen-release buried wire is formed by in-situ controlled hydrogenation of a magnesium-based alloy wire 1'. The magnesium-based alloy wire 1' is made of conventional magnesium-based alloys, including but not limited to Mg-Al, Mg-Zn, Mg-Re, Mg-Mn, Mg-Ca, Mg-Li, Mg-Sr, Mg-rare earth elements (such as Mg-Sc, Mg-Nd), etc., preferably containing Mg x Zn a and Mg x Ndb or magnesium-based multi-element alloy, preferably magnesium-based ternary alloy Mg x Zn a Nd b , wherein the specific composition and proportion of each element in the alloy can be adjusted within a reasonable range according to actual needs. Specifically, in the magnesium-based alloy wire, the Mg content is 95-98at.%, the Zn content is 0.5-3at.%, and the Nd content is 0.5-3at.%;

[0072] In the hydrogenation shell, at least Mg, MgH2, MgZn2 and NdH y phase, and the NdH y The grain size is 5-20 nm and is dispersed in the interior and surface of Mg. After controlled hydrogenation, the magnesium-based controlled hydrogen-release buried wire has better hydrogenation ability than pure magnesium buried wire.

[0073] After in-situ controlled hydrogenation, the magnesium-based controlled hydrogen-release embedded wire has a hydrogenated shell 2 covering the outer surface of the magnesium-based alloy wire 1' along the length direction, and the ratio of the radial thickness R1 of the hydrogenated shell 2 to the radius R2 of the internal unhydrogenated magnesium-based alloy wire 1' satisfies 0<R1 / R2≤4.5, preferably 0<R1 / R2≤1.5.

[0074] Preferably, the surface of the magnesium-based controlled hydrogen release buried wire has a nano-slow-down layer 3, which includes at least one of nano-magnesium oxide, nano-magnesium silicate, and nano-magnesium metasilicate. The thickness of the nano-slow-down layer 3 is 0.2-20 μm. Figure 2 .

[0075] The preparation method of the magnesium-based controlled hydrogen release embedded wire in the first and second embodiments is as follows: Figure 3 , including the following steps:

[0076] S1. smelting magnesium or magnesium-based alloy raw materials into ingots;

[0077] S2. The ingot is heated to 150-450° C., the punching rate is 0.2-0.5 mm / s, and air-cooled to obtain a cylindrical billet with a diameter of 1-10 mm and a length of 10-20 mm;

[0078] S3. Using a precision wire drawing machine and a multi-pass wire drawing die, the blank is subjected to multiple drawing processes to obtain a magnesium wire or a magnesium-based alloy wire with a diameter of 0.1-0.5 mm; preferably, the method further comprises the following steps:

[0079] S3.1. Anneal at 300-450°C for 15-45 minutes under an inert gas (such as argon) and cut into rough wires of 0.1-1.0 cm in length using a laser cutter.

[0080] S3.2. Use a high-speed polishing disc to fix the rough wire on the polishing fixture and polish it for 3-5 minutes to obtain a polished wire.

[0081] S3.3. Treat the polishing wire with acid, such as immersing it in dilute sulfuric acid or dilute phosphoric acid for 1-10 minutes to remove the surface oxide layer, then rinse with deionized water and dry.

[0082] S4. Subjecting the magnesium wire or magnesium-based alloy wire to an in-situ controlled hydrogenation treatment to obtain the magnesium-based controlled hydrogen-release embedded wire, wherein the in-situ controlled hydrogenation treatment is performed by at least one of the following methods:

[0083] 1) Under vacuum conditions (e.g. about 10 -4 Pa), introduce hydrogen, at a hydrogen pressure of 0.5-10 MPa, 100-450°C, preferably 200-400°C, and keep warm for 1-24h;

[0084] 2) Under vacuum conditions (e.g. about 10 -4 Pa), irradiating the magnesium wire or magnesium-based alloy wire with hydrogen plasma, the irradiation time is 0.5-60min, preferably 1-30min. The treatment conditions include: the temperature is below 100°C, preferably below 80°C, more preferably between room temperature and 50°C, using any one of microwave plasma (plasma excited by microwaves) and radio frequency plasma (plasma excited by radio frequency). The microwave power can be selected to be above 300W, and the microwave frequency can be selected to be above 0.5GHz, for example, 1-20GHz. The excitation frequency used in the generation of radio frequency plasma is generally above 10MHz. The reaction atmosphere of hydrogen plasma is usually hydrogen or a mixed gas of hydrogen and argon, for example, the volume ratio of hydrogen to argon is (20-50): (50-80).

[0085] Optionally, after step S4, there is further step S5 of forming a nano-slow-down layer on the surface of the magnesium-based controlled hydrogen-release embedded wire, and step S5 includes:

[0086] 1) dispersing the raw materials of the nano-slow-fall layer in an organic solvent (such as ethanol) to obtain a nano-dispersion liquid, preferably a nano-magnesium oxide dispersion liquid;

[0087] 2) applying (e.g., dipping, spraying, coating, etc.) the nano-dispersion onto the surface of the magnesium-based controlled hydrogen-release embedded wire;

[0088] 3) Drying at 120-150° C. for 20-40 minutes to form a magnesium-based controlled hydrogen-release embedded wire with a uniform and dense nano-slow-fall layer on the surface.

[0089] After step S5, the following steps may be optionally included:

[0090] S6, secondary annealing treatment, annealing the embedded wire at 300-450°C for 15-45 minutes under the protection of inert gas (such as argon);

[0091] S7. Sterilization treatment: Place the embedded thread on a sterilization tray and use a high-temperature and high-pressure steam sterilizer to sterilize under high-temperature and high-pressure conditions of 120-130°C for 20-60 minutes to obtain the finished embedded thread product. After cooling, sterile packaging is performed.

[0092] Example 1

[0093] The magnesium-based controlled hydrogen-release embedded wire of Example 1 uses magnesium wire as a substrate for in-situ controlled hydrogenation. The purity of the magnesium wire is 99.9%. The diameter of the magnesium-based controlled hydrogen-release embedded wire is 0.30±0.01 mm, the length is about 0.3 cm, and the controlled hydrogenation ratio is about 10%.

[0094] The preparation method of the magnesium-based controlled hydrogen release embedded wire comprises the following steps:

[0095] S1. Smelting high-purity magnesium metal into ingots;

[0096] S2. Preheat the ingot to 350°C, press at a rate of 0.3 mm / s, and air-cool to obtain a cylindrical billet with a diameter of about 2 mm and a length of 15 mm;

[0097] S3. Using a precision wire drawing machine and a multi-pass drawing die, the blank is drawn five times, wherein the diameter changes in the following order: ① from 2 mm to 1.0 mm, ② from 1.0 mm to 0.5 mm, ③ from 0.5 mm to 0.4 mm, ④ from 0.4 mm to 0.35 mm, and ⑤ from 0.35 mm to 0.32 mm, to obtain a magnesium wire with a diameter of approximately 0.32 mm, followed by the following steps:

[0098] S3.1. Anneal at 400°C for 30 min under argon protection and cut into 0.3 cm thick wires using a laser cutter.

[0099] S3.2. Using a high-speed polishing disc, fix the rough wire on the polishing fixture and polish it for 3 minutes to obtain a polished wire.

[0100] S3.3. Immerse the polishing wire in dilute sulfuric acid for 8 minutes to remove the surface oxide layer, rinse with deionized water, and dry.

[0101] S4. The magnesium wire is subjected to an in-situ controlled hydrogenation treatment, including: introducing hydrogen gas under a vacuum state, keeping the temperature at 400° C. at a hydrogen pressure of about 2±0.5 MPa, and maintaining the temperature for about 8 hours to obtain a magnesium-based controlled hydrogen-release buried wire with a diameter of about 0.30±0.01 mm and a length of about 0.3 cm.

[0102] Example 2

[0103] The difference between the magnesium-based controlled hydrogen release buried wire of Example 2 and Example 1 is that a nano-slow-down layer of about 2 μm is formed on the surface of the magnesium-based controlled hydrogen release buried wire, and step S5 is included after the aforementioned step S4:

[0104] 1) dispersing nano-magnesium oxide in ethanol to obtain a nano-dispersion liquid;

[0105] 2) dipping the magnesium-based controlled hydrogen-release embedded wire into a nano-dispersion liquid;

[0106] 3) Drying at 125° C. for 25 minutes to form a magnesium-based controlled hydrogen-release embedded wire having a uniform and dense nano-magnesium oxide slow-fall layer on the surface.

[0107] Example 3

[0108] The difference between the magnesium-based controlled hydrogen-release embedded wire of Example 3 and Example 2 is that the controlled hydrogenation ratio is different. The controlled hydrogenation ratio of this example is about 1%.

[0109] Example 4

[0110] The difference between the magnesium-based controlled hydrogen-release embedded wire of Example 4 and Example 2 is that the controlled hydrogenation ratio is different. The controlled hydrogenation ratio of this example is about 20%.

[0111] Example 5

[0112] The difference between the magnesium-based controlled hydrogen-release embedded wire of Example 5 and Example 2 is that the controlled hydrogenation method is different. In this method, hydrogen plasma radiation in-situ controlled hydrogenation is used. That is, step S4 includes:

[0113] The magnesium wire was irradiated with hydrogen plasma at room temperature and vacuum state, with the volume ratio of hydrogen to argon being 35:65. The irradiation treatment lasted for 10 minutes, and the hydrogenation ratio was about 10%.

[0114] The main parameters of Examples 1-5 are shown in Table 1:

[0115] Table 1

[0116]

[0117]

[0118] Examples 6-10

[0119] The magnesium-based controlled hydrogen release embedded wires of Examples 6-10 are made of magnesium-based ternary alloy Mg x Zn a Nd b The substrate has a Mg content of 97 at.%, a Zn content of 1.5 at.%, and a Nd content of 1.5 at.%. The preparation methods correspond to those in Examples 1-5, respectively. The specific parameters are shown in Table 2:

[0120] Table 2

[0121]

[0122] Comparative Example 1

[0123] Comparative Example 1 uses magnesium wire with a purity of 99.9%, a diameter of 0.30±0.01 mm, and a length of approximately 0.3 cm. The preparation method of Comparative Example 1 can refer to Example 1, but does not include the step of in-situ controlled hydrogenation of the magnesium wire.

[0124] Potentiodynamic polarization curve test

[0125] At 37°C, three wire samples from Examples 1-10 and Comparative Example 1 were randomly selected and electrochemically tested using linear sweep voltammetry (LSV). The experimental simulated body fluid was used as the electrolyte, with Examples 1-10 and Comparative Example 1 as the working electrodes, a platinum electrode as the counter electrode, a saturated calomel electrode as the reference electrode, and the electrolyte being simulated body fluid. The scanning voltage range was set to -2.0V to -1.0V, and the LSV curve was recorded to analyze the hydrogen evolution behavior and electrochemical stability of the magnesium hydride wire (see Table 3). The experiment was repeated three times. The polarization curves of Examples 1, 3-5, and Comparative Example 1 are shown in Table 3. Figure 4 shown.

[0126] Table 3: E of magnesium hydride wire and magnesium wire corr and i corr

[0127] sample <![CDATA[E corr / V]]> <![CDATA[i corr / μA·cm -2 ]]> Comparative Example 1 -1.805 378.93 Example 1 -1.724 257.16 Example 2 -1.681 143.35 Example 3 -1.690 274.87 Example 4 -1.789 98.027 Example 5 -1.663 159.53 Example 6 -1.698 246.85 Example 7 -1.640 128.56 Example 8 -1.610 210.48 Example 9 -1.575 78.215 Example 10 -1.618 113.650

[0128] From the experimental data, it can be seen that as the hydrogenation ratio increases, the corrosion potential of the material gradually shifts positively, indicating that its thermodynamic stability is enhanced. For example, the corrosion potential of pure magnesium in Comparative Example 1 is -1.805V, the corrosion potential of the magnesium wire treated with 10% hydrogenation in Example 1 rises to -1.724V, and the corrosion potential of the magnesium alloy wire in Example 6 rises to -1.698V. The degradation tendency of the material in the electrolyte is significantly reduced. In addition, the corrosion current density also decreases with the increase of the hydrogenation ratio. The corrosion current of the 10wt% hydrogenated sample in Example 1 is 257.16μA / cm 2 , relative to 378.93μA / cm of pure magnesium wire in comparative example 1 2 The reduction was 32.1%, while that in Example 6 was 34.9%. It can be seen that the hydrogenation treatment significantly inhibited the kinetic process of the corrosion reaction, effectively improved the corrosion resistance of the magnesium-based embedded wire, and increased the thermodynamic stability of the material.

[0129] According to Examples 1, 2, 6 and 7, at the same hydrogenation ratio, the nano-magnesium oxide coating further improves the corrosion resistance of the magnesium-based buried wire. The corrosion current of the uncoated sample in Example 1 is 257.16 μA / cm 2 , while the corrosion current of the sample with nano-coating added in Example 2 was reduced to 143.35 μA / cm 2 , a decrease of 44.3% compared with Example 1. The decrease of Example 7 compared with Example 6 reached 47.9%. This optimization is mainly attributed to the fact that the uniform and dense nano-magnesium oxide layer can effectively block the contact between the electrolyte and the magnesium substrate, thereby delaying the corrosion process.

[0130] In terms of the hydrogenation ratio, Example 4, with a hydrogenation ratio of 20%, further reduced the corrosion current by 31.6% compared to Example 2, with a hydrogenation ratio of 10%. A similar effect was observed using magnesium-based alloy wire, with the overall corrosion current decreasing as the hydrogenation ratio increased. However, considering the mechanical properties of the material, excessively high hydrogenation levels can easily lead to increased material brittleness, making it difficult to ensure hydrogenation uniformity, potentially leading to undesirable localized cracking and affecting mechanical reliability in practical applications. Based on the performance of magnesium wire and magnesium alloy wire, and after extensive experiments, the hydrogenation ratio of magnesium wire is preferably controlled below 20%, while the hydrogenation ratio of magnesium-based alloy wire can be slightly higher, preferably below 30%. Therefore, a hydrogenation ratio of 1 to 30% combined with a nanocoating is a preferred comprehensive approach, ensuring a controllable and appropriate degradation rate while maintaining sufficient mechanical strength.

[0131] When the hydrogenation ratio is the same as 10%, when hydrogen plasma is used for hydrogenation treatment, the corrosion potential of Example 5 increases from -1.681V in Example 2 to -1.663V, and the corrosion potential of Example 10 increases from -1.640V in Example 7 to -1.618V, indicating that the plasma in-situ controlled hydrogenation method helps to further reduce the degradation tendency of the material in the electrolyte, and the hydrogenation reaction can be carried out at room temperature with high reaction efficiency and rate, which is an advanced means for efficiently preparing magnesium-based controlled hydrogen-release buried wires.

[0132] Although preferred embodiments of the present invention have been described, further changes and modifications may be made to these embodiments by those skilled in the art once the basic inventive concepts are understood. Therefore, the present invention is intended to include the preferred embodiments as well as all changes and modifications that fall within the scope of the present invention. Obviously, various changes and modifications may be made to the present invention by those skilled in the art without departing from the spirit and scope of the present invention.

Claims

1. A magnesium-based controlled hydrogen release embedded wire, characterized in that: The magnesium-based controlled hydrogen-release embedded wire is formed by in-situ controlled hydrogenation of a magnesium wire or a magnesium-based alloy wire; The purity of magnesium wire is above 99%; The magnesium-based alloy includes at least one of a magnesium-based binary alloy and a magnesium-based multi-component alloy; The diameter of the magnesium wire or magnesium-based alloy wire is 0.1-0.5 mm, and the controlled hydrogenation ratio is greater than 0 and less than 80%.

2. The magnesium-based controlled hydrogen-release embedded wire according to claim 1, characterized in that: After in-situ controlled hydrogenation, the magnesium-based controlled hydrogen-release embedded wire has a hydrogenated shell covering the outer surface of the magnesium wire or magnesium-based alloy wire along the length direction, and the ratio of the radial thickness R1 of the hydrogenated shell to the radius R2 of the internal unhydrogenated magnesium wire or magnesium-based alloy wire satisfies: 0<R1 / R2≤4.

5.

3. The magnesium-based controlled hydrogen-release embedded wire according to claim 1 or 2, characterized in that: The magnesium-based alloy wire meets at least one of the following conditions: 1) The magnesium-based alloy is a magnesium-based binary alloy, including at least one of Mg-Al, Mg-Zn, Mg-Re, Mg-Mn, Mg-Ca, Mg-Li, Mg-Sr, and Mg-rare earth elements; 2) The magnesium-based alloy is a magnesium-based binary alloy Mg x Zn a and Mg x Nd b combination of; 3) The magnesium-based alloy is a magnesium-based ternary alloy Mg x Zn a Nd b .

4. The magnesium-based controlled hydrogen release embedded wire according to claim 3, characterized in that: The magnesium-based alloy wire meets at least one of the following conditions: 1) In the magnesium-based alloy wire, the Mg content is 95-98 at.%, the Zn content is 0.5-3 at.%, and the Nd content is 0.5-3 at.%; 2) In the hydrogenation shell, at least Mg, MgH2, MgZn2 and NdH y phase, and the NdH y The grain size is 5-20nm and is dispersed inside and on the surface of Mg.

5. The magnesium-based controlled hydrogen-release embedded wire according to claim 3, characterized in that: The surface of the magnesium-based controlled hydrogen-release buried wire has a nano-slow-down layer comprising at least one of magnesium oxide, magnesium silicate, and magnesium metasilicate. The thickness of the nano-slow-down layer is 0.2-20 μm.

6. The magnesium-based controlled hydrogen-release embedded wire according to claim 4 or 5, characterized in that: The hydrogen release rate of the magnesium-based controlled hydrogen-release embedded wire is greater than 0 and less than or equal to 10.0 ml / h×cm 2 , the hydrogen release time is greater than 0 and less than or equal to 5 weeks.

7. A method for preparing the magnesium-based controlled hydrogen release embedded wire according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1. smelting magnesium or magnesium-based alloy raw materials into ingots; S2, extruding the ingot into a billet; S3. Drawing the blank to obtain magnesium wire or magnesium-based alloy wire; S4. Performing an in-situ controlled hydrogenation treatment on the magnesium wire or magnesium-based alloy wire to obtain the magnesium-based controlled hydrogen-release embedded wire.

8. The preparation method according to claim 7, wherein Meet at least one of the following: 1) In step S2, the ingot is heated to 150-450° C. and the punching rate is 0.2-0.5 mm / s to obtain a cylindrical billet with a diameter of 1-10 mm and a length of 10-20 mm; 2) In step S3, the blank is subjected to multiple drawing processes to obtain a magnesium wire or a magnesium-based alloy wire with a diameter of 0.1-0.5 mm; 3) In step S4, the magnesium wire or magnesium-based alloy wire is subjected to an in-situ controlled hydrogenation treatment using hydrogen at a hydrogen pressure of 0.5-10 MPa, a holding time of 1-24 h, and a temperature of 100-450° C.; or The magnesium wire or magnesium-based alloy wire is irradiated with hydrogen plasma to perform in-situ controlled hydrogenation treatment, with the irradiation time being 0.5-60 minutes.

9. The preparation method according to claim 8, wherein After step S4, there is also a step of forming a nano slow-down layer on the surface of the magnesium-based controlled hydrogen-release buried wire, including: 1) dispersing the raw materials of the nano-slow-fall layer in an organic solvent to obtain a nano-dispersion liquid; 2) applying the nano-dispersion to the surface of the magnesium-based controlled hydrogen-release embedded wire; 3) Drying to form a magnesium-based controlled hydrogen-release embedded wire with a nano-slow-fall layer on the surface.

10. Use of the magnesium-based controlled hydrogen-release catgut embedding method according to any one of claims 1 to 6, or the magnesium-based controlled hydrogen-release catgut embedding method obtained according to any one of claims 7 to 9, in preparing a catgut embedding therapy device.

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